CN112707791B - Method for producing cyclohexanol and cyclohexanone mixture by using cyclohexyl hydroperoxide - Google Patents
Method for producing cyclohexanol and cyclohexanone mixture by using cyclohexyl hydroperoxide Download PDFInfo
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Abstract
A method for producing a mixture of cyclohexanol and cyclohexanone by using cyclohexyl hydroperoxide comprises the steps of carrying out non-catalytic oxidation on cyclohexane by using molecular oxygen to generate a cyclohexyl hydroperoxide-containing cyclohexane oxidation solution, and then carrying out subdivision to generate a mixture of cyclohexyl hydroperoxide and cyclohexanone, wherein when the cyclohexyl hydroperoxide-containing cyclohexane oxidation solution is decomposed, a two-step decomposition process combining an acidic quasi-homogeneous catalytic decomposition process and a sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is adopted: (1) Atomizing the transition metal catalyst solution by using compressed gas through a Venturi atomizer, then mixing the atomized transition metal catalyst solution and cyclohexane oxidation solution together through a Venturi mixer, and then, entering a decomposition system for acidic quasi-homogeneous catalytic decomposition to obtain a decomposition solution; (2) And carrying out heterogeneous catalytic decomposition on the decomposition solution in a sodium hydroxide alkaline aqueous solution. The method can lead the concentration of the cyclohexyl hydroperoxide in the final decomposition liquid to be lower than 100ppm, and improve the integral conversion rate of the cyclohexyl hydroperoxide decomposition reaction.
Description
Technical Field
The invention relates to a method for producing a mixture of cyclohexanol and cyclohexanone, in particular to a method for producing the mixture of cyclohexanol and cyclohexanone by a two-step decomposition reaction of cyclohexane oxidation solution containing cyclohexyl hydroperoxide.
Background
Cyclohexane oxidation is a widely used process in the industry for preparing mixtures of cyclohexanol and cyclohexanone. In this method, cyclohexane is first directly oxidized by air under non-catalytic conditions to produce a mixture containing cyclohexylhydroperoxide, cyclohexanol, cyclohexanone, acids, esters, etc., and then the cyclohexylhydroperoxide in this mixture is catalytically decomposed to produce cyclohexanol and cyclohexanone. The produced cyclohexanol and cyclohexanone can be further oxidized to produce adipic acid, and pure cyclohexanone can be produced by purification and cyclohexanol dehydrogenation to produce caprolactam. Adipic acid and caprolactam are the main raw materials for producing polyamide high molecular materials.
Numerous examples and literature reports indicate that optimization of both the cyclohexane oxidation section and the cyclohexyl hydroperoxide decomposition section is necessary and is more important if higher yields of alcohol ketone are to be obtained from the cyclohexane oxidation process. In the case of the cyclohexane oxidation section, the oxidation must be controlled at low conversion rates (.ltoreq.3.5%) because of the free radical chain reaction mechanism employed, to reduce the side reactions of the intermediate product cyclohexyl hydroperoxide produced by the oxidation which continue to be deeply oxidized to acid and ester impurities. From the aspect of the cyclohexyl hydroperoxide decomposition section, the decomposition reaction must achieve high decomposition yield and high conversion rate at the same time, so that the efficiency of the whole process can be improved (see further research and development of cyclohexane oxidative decomposition process technology, jianhua, trichlorphon, chemical engineering, 2010, 38,2, 98-102).
There are three main routes to the decomposition process of cyclohexylhydroperoxide that have been successfully industrialized worldwide:
the first is a single aqueous NaOH solution cyclohexyl hydroperoxide heterogeneous decomposition process, under the condition of higher alkalinity, OH - The concentration is more than 1mol/L, the temperature is controlled at 90-100 ℃, the decomposition conversion rate of the cyclohexyl hydroperoxide can reach more than 99.7%, but the yield of the decomposed alcohol ketone is not high, and only 84-86%;
the second is a transition metal catalyzed cyclohexyl hydroperoxide homogeneous decomposition process under a single acidic condition, the temperature is controlled to be 90-94 ℃, the homogeneous decomposition yield of cyclohexyl hydroperoxide can reach more than 94% under the catalysis of oily chromate, but the decomposition conversion rate is only about 92%, and the total yield of alcohol ketone is only 92% multiplied by 94% = 86.5% because the undegraded 8% cyclohexyl hydroperoxide is completely lost under the working condition of high Wen Gaochun ketone after alkane rectification;
the third route is that the three-step decomposition process of cyclohexyl hydroperoxide disclosed in CN102627525B utilizes the high decomposition yield of acid homogeneous decomposition and the high decomposition conversion rate characteristic of heterogeneous decomposition, and the two decomposition processes are connected in series and successfully implemented on a 12-ten thousand ton/year cyclohexanone device in China, so that the consumption of raw materials of the device is reduced by more than 4 percent. However, industrial equipment for the acid homogeneous decomposition process of cyclohexyl hydroperoxide requires that the transition metal salt catalyst be soluble in the cyclohexane organic phase to form a homogeneous reaction system, so that naphthenate, octanoate, stearate and esters of transition metal acids are generally used as the decomposition catalyst.
It has been reported that in a small test of homogeneous decomposition of pure cyclohexylhydroperoxide using chromium ions, the conversion of cyclohexylhydroperoxide can be up to 99% or more and the selectivity of cyclohexanone can be almost up to 98% by the route of formation of the intermediate of the transition metal cyclohexylhydroperoxide complex (see Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous Cr) VI Catalysis Optimizing the Reaction by Evaluating the Reaction Mechanism, hamann et al, chemCatchem,2018,10,2755-2767). However, in practical large-scale production devices, for example, a complete set of devices for preparing cyclohexanol and cyclohexanone by oxidizing cyclohexane introduced from France in the last 80 th century of China, the conversion rate of cyclohexyl hydroperoxide can only reach about 92% by taking chromium ions as a catalyst, the total yield of cyclohexanone and cyclohexanol in a homogeneous decomposition process flow is only 86.5%, and the ratio of cyclohexanone to cyclohexanol is only 2:1. Therefore, the actual production situation is inconsistent with the condition of the pilot scale, and the ideal homogeneous decomposition process is not carried out in the actual production device.
Research shows that the reason why the ideal homogeneous decomposition is not carried out in the actual production situation is mainly that the following three points are: 1) The transition metal catalyst is unstable under the reaction condition and is extremely easy to thermally decompose, so that transition metal oxide precipitates are generated. In the large-scale production process, the catalyst solution is directly added into a homogeneous decomposition system at 90-94 ℃ through a pipeline, the diffusion and dissolution speed of the catalyst solution in the decomposition liquid is relatively slower than the thermal decomposition speed of the catalyst solution, and the transition metal homogeneous catalyst starts to thermally decompose under the condition that the transition metal homogeneous catalyst is not well mixed with the decomposition liquid; 2) Because the initial transition metal homogeneous catalyst has high local concentration, the transition metal oxide generated by decomposition of the catalyst is insoluble in cyclohexane phase and is easy to coalesce into solid particles with larger volume, and the transition metal oxide precipitate is generated, so that the catalyst can not be uniformly dissolved and distributed; 3) The scale inhibitor has limited protection effect on the extraction and complexation of transition metal ions with high local concentration, a small amount of transition metal ions can be combined with organic acid, and the transition metal ions are precipitated in the form of salt and attached to the inner wall of equipment after dehydration.
In all the above cases, the homogeneous decomposition process is heterogeneous, and the reactivity of the homogeneous decomposition catalyst is reduced, so that a part of cyclohexyl hydroperoxide is decomposed in a free radical mode, and the ketol ratio and the reaction yield are lower than expected. In addition, the precipitation of the catalyst, the polymerization of free radicals and the mixing of organic acid can also form a large amount of insoluble substances attached to the inner wall of the equipment, and when the insoluble substances are too much, the pipeline and the pump can be blocked, so that the continuous production is affected.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for producing a mixture of cyclohexanol and cyclohexanone by using cyclohexyl hydroperoxide, which can ensure that a catalyst is stably and uniformly distributed in decomposition liquid, improve the decomposition conversion rate and yield of cyclohexyl hydroperoxide and prolong the operation period of a decomposition system.
The technical scheme adopted for solving the technical problems is that in the method for producing the mixture of cyclohexanol and cyclohexanone by using cyclohexyl hydroperoxide, firstly, cyclohexane is subjected to non-catalytic oxidation by using molecular oxygen to generate cyclohexyl hydroperoxide-containing cyclohexane oxidation solution, and then the cyclohexyl hydroperoxide is decomposed to generate the mixture of cyclohexyl hydroperoxide and cyclohexanone, and the method is characterized in that when the cyclohexyl hydroperoxide-containing cyclohexane oxidation solution is decomposed, a two-step decomposition process combining an acidic quasi-homogeneous catalytic decomposition process and a sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is adopted:
(1) Atomizing the transition metal catalyst solution by using compressed gas through a Venturi atomizer, then mixing the atomized transition metal catalyst solution and cyclohexane oxidation solution containing cyclohexyl hydroperoxide through a Venturi mixer, and then, entering a decomposition system for acidic quasi-homogeneous catalytic decomposition to obtain a decomposition solution;
(2) And (3) carrying out heterogeneous catalytic decomposition on the decomposition solution obtained in the step (1) in a sodium hydroxide alkaline aqueous solution to obtain a mixture of cyclohexanol and cyclohexanone.
Further, in the decomposition process step (1), the transition metal catalyst is a water-soluble salt formed by one or more transition metals of chromium, cobalt, iron, manganese, molybdenum and vanadium, preferably 1-3 wt% chromic acid aqueous solution. Chromium has high selectivity for catalyzing cyclohexanone decomposed by cyclohexyl hydroperoxide, and chromic acid aqueous solution can be directly prepared by dissolving chromic anhydride in water.
Further, in the decomposition process step (1), the transition metal catalyst is an oil-soluble ester or salt formed by one or more transition metals of chromium, cobalt, iron, manganese, molybdenum and vanadium.
In the decomposition process step (1), when the conventional oil-soluble transition metal salt or ester is used as a catalyst, theory and practice prove that the conventional oil-soluble transition metal salt or ester catalyst is unstable in a reaction system, and a pure homogeneous decomposition system is formed. Thus, in addition to the oil soluble transition metal salts or esters catalysts, water soluble transition metal salts may be used to catalyze the decomposition of cyclohexylhydroperoxide in the cyclohexane organic phase, the transition metal cations may be chromium, cobalt, iron, manganese, molybdenum, vanadium, and the like, and the anions may be hydroxide, carboxylate, sulfonate, and the like.
In the decomposition process step (1), the dosage of the transition metal catalyst is 4-20 ppm of the mass of the cyclohexane oxidation solution.
Further, in the step (1) of the decomposition process, 1-hydroxyethylidene-1, 1-diphosphonate needs to be added in the process of catalytic decomposition. 1-hydroxy ethylidene-1, 1-diphosphonate is used as dispersant and scale inhibitor of the reaction system.
Further, in the decomposition process step (1), the mass ratio of the 1-hydroxyethylidene-1, 1-diphosphonate to the transition metal catalyst is 1:0.6 to 1.4.
Further, in the decomposition process step (1), the decomposition temperature is 90-100 ℃. So that the catalyst can be distributed in the form of nano particles in the reaction system in a short time.
Further, in the decomposition process step (2), OH of the alkaline aqueous solution - The molar concentration of (C) is 0.5-1.0mol/L.
Further, in the decomposition process step (2), the heterogeneous catalytic decomposition temperature is 95-105 ℃.
Preferably, after a cyclohexane oxidation solution containing 3 to 5wt% of cyclohexyl hydroperoxide (the material is called a decomposition solution after entering a decomposition system) is subjected to heat exchange, the temperature is reduced to 110 to 120 ℃; with 1.0-1.3 MpaG of compressed inert gas (gas may be N) 2 Homogeneously decomposed compressed off-gas and oxidized off-gas) of 100Nm 3 H passing through a venturi atomizer, sucking in an aqueous solution containing a transition metal catalyst and a solution of 1-hydroxyethylidene-1, 1-bisphosphonate due to a negative pressure generated by a maximum flow rate of the compressed gas at the venturi throat, forming a compressed gas stream containing atomized liquid particles of the catalyst at the venturi outlet; then, the compressed gas flow is mixed with cyclohexane oxidation liquid containing cyclohexyl hydroperoxide by a Venturi mixer and enters the tower bottom of the decomposition reaction rectifying tower together.
In a preferred scheme, chromic anhydride is dissolved in water to prepare a chromic acid aqueous solution containing 1-3 wt% of chromium, and a cyclohexane solution containing 2-4-wt% of 1-hydroxyethylidene-1, 1-diphosphonate is prepared at the same time, wherein the weight ratio of the chromic anhydride in the chromic acid aqueous solution to the 1-hydroxyethylidene-1, 1-diphosphonate in the 1-hydroxyethylidene-1, 1-diphosphonate cyclohexane solution is 1:1.
In the preferred scheme, in the decomposing rectifying tower kettle, the normal pressure acid decomposing system temperature is 90-100 ℃, the azeotropic temperature of cyclohexane and water under the pressure of the system (25-60 KpaG) is 75-83 ℃, water in the decomposing system (water in chromic acid water solution and water generated after the decomposition of cyclohexyl hydrogen peroxide) and cyclohexane in the decomposing liquid are quickly azeotroped and vaporized, and the materials in the reaction are strongly stirred and mixed by the expansion of compressed gas. After the chromic acid aqueous solution drops of the catalyst are heated, the chromic acid aqueous solution drops are continuously broken into smaller drops, the micro-nano drops are uniformly distributed in a reaction system, and as the system temperature continues to rise, the chromic acid micro-nano drops are continuously dried to lose water molecules, and under the protection of 1-hydroxyethylidene-1, 1-diphosphonate, chromic anhydride is finally uniformly distributed in an organic phase of a decomposition system in a molecular level or nano level particle mode, so that a quasi-homogeneous decomposition environment is formed. And part of cyclohexane and free water evaporated by the vaporization heat and the reaction heat are discharged from the top of the decomposition rectifying tower, and the content of cyclohexanol, cyclohexanone and impurities in the cyclohexane at the top of the tower is controlled by utilizing reflux, so that the cyclohexane is ensured to return to an oxidation process without causing the increase of oxidation side reactions.
In the preferred scheme, in order to increase the conversion rate of the acid quasi-homogeneous decomposition, the decomposition liquid in the decomposing rectifying tower kettle is fully decomposed in a homogeneous decomposition reactor, the homogeneous decomposition reactor is designed into 1-4 reaction chambers, the residence time of the homogeneous decomposition reaction is increased to 25-40 minutes, the reactor pressure is normal pressure, and the temperature is controlled to be 90-100 ℃. The gas phase of the reactor is communicated with the tower kettle of the decomposing and rectifying tower, and each reaction chamber can be provided with a stirring or steam heating device so as to continuously maintain and strengthen the dispersion of the catalyst. The reaction chamber may also be supplemented with a cyclohexane solution of 1-hydroxyethylidene-1, 1-diphosphonate to further prevent the formation of transition metal insolubles.
The core innovation points of the invention are as follows: the mode of catalyst addition was changed. Firstly, sucking a catalyst dilute aqueous solution by using compressed gas through a venturi atomizer, wherein the catalyst dilute aqueous solution is continuously crashed in the venturi throat due to the venturi effect, atomized catalyst droplets are formed in the gas at the outlet of the venturi, and the droplets containing the catalyst are uniformly distributed in the compressed gas with the diameter of 10-50 microns; then, the compressed gas containing atomized catalyst micro-droplets is mixed with cyclohexane oxidizing solution through a Venturi mixer and then enters a normal-pressure homogeneous decomposition system for acid quasi-homogeneous catalytic decomposition; and then, carrying out heterogeneous catalytic decomposition on the decomposition solution obtained by the acidic quasi-homogeneous catalytic decomposition in a sodium hydroxide alkaline aqueous solution to obtain a mixture of the cyclohexanol and the cyclohexanone.
The invention mixes the compressed gas containing atomized catalyst micro-droplets with cyclohexane oxidizing solution through a Venturi mixer and then enters a normal pressure homogeneous decomposition system for decomposition, and the working principle is as follows: 1) The temperature of the catalyst drops rises relatively slowly in the mixing process of the Venturi mixer due to the protection of the gas thermal resistance effect, so that the phenomena of thermal decomposition and drying agglomeration caused by overlarge local concentration of the catalyst in the mixing process are avoided; 2) After the cyclohexane oxidizing solution and the catalyst liquid drops surrounding the compressed gas are mixed by a mixer, the mixture enters a decomposition reaction system with relatively low pressure, and the system continuously generates intense stirring and mixing due to the expansion of the gas and the flash evaporation effect of a large amount of cyclohexane, so that the diffusion distribution speed of the catalyst liquid drops in the reaction system is greatly accelerated; 3) The water-soluble transition metal salt catalyst is rapidly dispersed along with the catalyst liquid drops in a reaction system, the surfaces of the catalyst liquid drops touch a high-temperature cyclohexane phase, a severe water-alkyl azeotropy occurs at the contact interface between the catalyst liquid drops and the cyclohexane, the catalyst liquid drops are crushed to smaller sizes again by the generated external-to-internal impact, in addition, as the temperature in the catalyst liquid drops continuously rises, bubbles are rapidly formed in the catalyst liquid drops due to a small amount of dissolved gas in the atomization process of compressed gas, and the bubbles are rapidly evaporated along with the rapid evaporation of a solvent, so that cavitation effect occurs, a large number of micro-jet and shock waves from inside to outside are generated, and the catalyst liquid drops are further crushed, so that the particle sizes of the catalyst liquid drops are crushed to micro-nano sizes; 4) The micro-nano catalyst droplets are uniformly dispersed in a cyclohexane phase, and then are continuously dried and thermally decomposed to form 10-100 nano transition metal catalyst particles, and meanwhile, the 1-hydroxyethylidene-1, 1-diphosphonate is subjected to surface modification of nano particles, so that the nano particles can stably exist in a reaction system for a long time, and the effect of catalyzing and decomposing cyclohexyl hydrogen peroxide is achieved.
The catalyst of the invention has four stages in the use process: 1) atomizing 2) dispersing 3) crushing 4) stabilizing. The micro-nano catalyst liquid drops are dried and thermally decomposed, so that the formed nano transition metal catalyst particles have large specific surface area, and atoms on the surfaces of the nano transition metal catalyst particles have higher reactivity and can be equivalent to the level of homogeneous decomposition. The present inventors named such a reaction system as a quasi-homogeneous decomposition system.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional homogeneous decomposition reaction, the use mode of the catalyst accelerates the dispersion speed of the catalyst, and avoids the occurrence of thermal decomposition or dry agglomeration of the catalyst to form large-size oxide particle precipitation under the condition of overlarge local concentration of the catalyst in the mixing process;
(2) The quasi-homogeneous decomposition system has the advantages that the specific surface area of the nano-scale transition metal catalyst particles is large, the surface atoms of the nano-scale transition metal catalyst particles have higher reactivity, the level of homogeneous decomposition can be close to that of the homogeneous decomposition, and the higher decomposition conversion rate and cyclohexanone selectivity of the nano-scale transition metal catalyst particles can be ensured;
(3) After 70-90% of cyclohexyl hydroperoxide is decomposed in the first step of the acidic quasi-homogeneous decomposition process; and secondly, decomposing the decomposition solution containing the undegraded cyclohexyl hydroperoxide in the sodium hydroxide alkaline aqueous solution at a low temperature in a heterogeneous catalytic way, so that the concentration of the cyclohexyl hydroperoxide in the final decomposition solution is lower than 100ppm, the decomposition conversion rate reaches 99.7%, the total decomposition yield reaches 93%, and the conversion rate of the integral cyclohexyl hydroperoxide decomposition reaction is improved.
Drawings
FIG. 1 is a schematic diagram of the apparatus and process used in the decomposition of cyclohexylhydroperoxide of examples 1 and 2 of the present invention by a two-step decomposition process combining an acidic quasi-homogeneous catalytic decomposition process with a sodium hydroxide aqueous alkaline solution heterogeneous catalytic decomposition process.
In the figure: 11-venturi atomizer, 12-venturi mixer, 13-decomposition rectifying tower, 14-decomposition reactor, 15-condensation cooling separator, 21-heterogeneous decomposition tower, 22-heterogeneous decomposition separator, 110-inert gas, 111-chromic acid aqueous solution catalyst, 112-cyclohexane solution containing 1-hydroxyethylidene-1, 1-diphosphonate 3.5 wt%, cyclohexane oxidation solution containing cyclohexyl hydrogen peroxide after heat exchange by 120-oxidative decomposition heat exchanger, 132-cyclohexane, water vapor and inert gas coming out from top of decomposition rectifying tower, 133-decomposition solution containing catalyst nano-particles, scale inhibitor, 141-decomposition solution, 142-cyclohexane and a small amount of acid water vapor, 151-cyclohexane liquid as reflux liquid, 152-cyclohexane liquid at cyclohexane oxidation section, 153-acidic aqueous solution, 154-inert non-condensable gas, 210-32% fresh alkali water mixture from fresh alkali pump, 211-decomposition solution and alkali water mixture, 221-waste alkali solution containing 70ppm of cyclohexyl hydrogen peroxide, 222-alkali lye, 223-waste alkali solution.
FIG. 2 is a schematic diagram of the apparatus and process flow used in the two-step decomposition process of the combination of the quasi-homogeneous catalytic decomposition process of acid and the heterogeneous catalytic decomposition process of aqueous alkaline solution of sodium hydroxide according to the invention after concentration, washing and dehydration of the cyclohexane oxidation solution containing cyclohexyl hydroperoxide of example 3 of the invention.
In the figure: 01-condensation cooling separator, 02-pre-concentration tower, 03-washing tower, 11-Venturi atomizer, 13-dehydration tower, 14-homogeneous decomposition reactor, 15-dehydration tower top condensation cooling separator, 21-heterogeneous decomposition tower, 22-heterogeneous decomposition separator, 011-cyclohexane reflux, 012-cyclohexane liquid of cyclohexane oxidation section, 013-acid aqueous solution, 014-noncondensable gas, 020-cyclohexane oxidation solution, 021-cyclohexane oxidation solution after concentrating in pre-concentration tower kettle, 022-noncondensable gas, 030-desalted water, 031-cyclohexane oxidation solution, 032-washing water, 033-cyclohexane, 110-compressed noncondensable gas, the catalyst comprises (by weight ratio) a catalyst of tert-butyl 111-chromate solution, (by weight ratio) a cyclohexane solution containing 3.5. wt% of 1-hydroxyethylidene-1, 1-diphosphonate, (by weight ratio) a cyclohexane solution containing 131-cyclohexane oxidation solution, (by weight ratio) 132-cyclohexane and a small amount of water vapor, (by weight ratio) 141-decomposition solution obtained by quasi-homogeneous decomposition, (by weight ratio) 142-cyclohexane and a small amount of water vapor, (by weight ratio) 151-cyclohexane liquid as reflux liquid, (by weight ratio) 152-cyclohexane liquid obtained by the cyclohexane oxidation section, (by weight ratio) 153-acidic aqueous solution, (by weight ratio) 154-inert non-condensable gas, (by weight ratio) 210-new alkali liquid from a new alkali pump, (by weight ratio) 211-mixed liquid obtained by heterogeneous decomposition and alkali liquid, (by weight ratio) 221-decomposition solution containing 70ppm of cyclohexyl hydroperoxide, (by weight ratio) 222-waste alkali liquid and 223-waste alkali liquid.
FIG. 3 is a schematic view of an apparatus and a process flow used in the decomposition of cyclohexylhydroperoxide of comparative example 1 using the decomposition procedure disclosed in CN 102627542B.
In the figure: 13-decomposing and rectifying tower, 14-decomposing reactor, 15-condensing and cooling separator, 21-heterogeneous decomposing first decomposing tower, 22-heterogeneous first decomposing separator, 23-heterogeneous second decomposing tower, 24-heterogeneous second decomposing separator, 130-cyclohexane oxidizing liquid containing cyclohexyl hydrogen peroxide after heat exchange by decomposing heat exchanger, 111-homogeneous decomposing catalyst tert-butyl chromate solution, 112-1-hydroxy ethylidene-1, 1-diphosphonate solution, 133-decomposing liquid containing catalyst and scale inhibitor, 134-distilled cyclohexane, small amount of acid water and inert gas, 141-4 chamber decomposing liquid, 142-cyclohexane gas distilled from the homogeneous decomposition reactor is equal, 151-cyclohexane liquid used as reflux liquid, 152-cyclohexane liquid used for removing cyclohexane oxidation section, 153-acid aqueous solution, 154-inert non-condensable gas, 210-new alkali liquor from 32% new alkali pump, 211-mixed liquid of decomposition liquid and alkali water after heterogeneous first-step decomposition, 221-decomposing liquid containing 0.06% of cyclohexyl hydrogen peroxide, 222-circulating alkali liquid, 223-waste alkali liquid, 230-32% alkali liquid of a new alkali pump, 231-decomposing liquid and alkali water mixed liquid, 241-decomposing liquid containing less than 70ppm of cyclohexyl hydrogen peroxide, 242/243-circulating alkali.
FIG. 4 is a schematic diagram of the apparatus and process flow used in comparative example 2 in which the introduced process flow of homogeneous decomposition of cyclohexylhydroperoxide from French Rodinia was such that the cyclohexylhydroperoxide-containing cyclohexane oxide solution was concentrated, washed with water and dehydrated before entering the homogeneous decomposition.
In the figure: 01-a condensation cooling separator at the top of the preconcentration tower, 02-a preconcentration tower, 03-a washing tower, 13-a dehydration tower, 14-a homogeneous decomposition reactor, 15-a condensation cooling separator at the top of the dehydration tower, 011-cyclohexane reflux, 012-cyclohexane liquid at a cyclohexane oxidation section, 013-acid aqueous solution, 014-non-condensable gas, 020-cyclohexane oxidation liquid, 021-cyclohexane oxidation liquid concentrated by the preconcentration tower, 022-non-condensable gas, 030-desalted water, 031-washed cyclohexane oxidation liquid, 032-washing water, 033-cyclohexane, 131-cyclohexane oxidation liquid, 132-cyclohexane and water vapor, 111-chromium-containing 3wt% of tert-butyl chromate catalyst solution, 112-phosphoric acid Xin Zhizu scale agent, 141-decomposed solution, 142-cyclohexane and a small amount of water vapor, 151-cyclohexane liquid as reflux, 152-cyclohexane liquid at a cyclohexane oxidation section, 153-acid aqueous solution, 154-inert non-condensable gas.
Detailed Description
The invention will be further described with reference to specific examples and figures.
Example 1
Referring to fig. 1, when the cyclohexyl hydroperoxide of the present embodiment is decomposed, a two-step decomposition process combining an acidic quasi-homogeneous catalytic decomposition process and a sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is as follows:
(1) A73. 73 Kg/h aqueous chromic acid catalyst 111 containing 3% by weight of chromium was mixed with a 121. 121 Kg/h cyclohexane solution 112 containing 3.5. 3.5 wt% of 1-hydroxyethylidene-1, 1-diphosphonate (scale inhibitor) at 100Nm of 1.2 MpaG from the outlet of a tail gas compressor in a venturi atomizer 11 3 Atomizing/h inert gas 110 to form a gas mixture containing tiny catalyst solution particles, feeding the gas mixture into a Venturi mixer 12 together with 436500 Kg/h cyclohexane oxidation solution 120 (pressure 1.2 MpaG and temperature 120 ℃) containing cyclohexyl hydrogen peroxide which is subjected to heat exchange from an oxidative decomposition heat exchanger, fully mixing, feeding the mixture into a decomposition rectifying tower 13 kettle, carrying out acidic quasi-homogeneous catalytic decomposition at the pressure of 25-60 KpaG and the temperature of 90-95 ℃ on the decomposition rectifying tower 13 kettle, feeding a decomposition solution 133 containing catalyst nano particles and a scale inhibitor after passing through the decomposition rectifying tower 13 kettle into a decomposition reactor 14, sequentially flowing from 1 chamber, 2 chambers and 3 chambers to 4 chambers, and carrying out residence time of 30 minutes to reach a set valueThe decomposition conversion rate is 80 percent, and a decomposition solution 141 is obtained;
the cyclohexane is vaporized by the reaction heat, the cyclohexane and a small amount of acid water vapor 142 are brought into the decomposition rectifying tower 13 through a gas phase pipe, the cyclohexane, the water vapor and the inert gas 132 which are discharged from the top of the decomposition rectifying tower 13 are condensed, cooled and separated through a condensation cooling separator 15, 52000Kg/h cyclohexane is used as reflux 151, 130000 Kg/h cyclohexane 152 is sent back to the previous cyclohexane oxidation section, 1380 Kg/h acidic aqueous solution 153 is sent to the waste lye of heterogeneous decomposition for neutralization, 900Nm 3 The/h inert non-condensable gas 154 is sent to a tail gas compressor, part of the inert non-condensable gas is returned to a catalyst feeding system to atomize catalyst solution after being pressurized by the compressor, and part of the inert non-condensable gas is sent to tail gas treatment;
(2) 305130Kg/h of decomposing solution 141 (containing 0.8% of cyclohexyl hydroperoxide) obtained by quasi-homogeneous decomposition in the decomposing process step (1) is mixed with 4200Kg/h of neo-alkali 210 and 78000Kg/h of circulating alkali 222 in a heterogeneous decomposing tower 21, and then decomposed under the action of catalyst to decompose OH in alkaline aqueous solution by heterogeneous catalysis - The molar concentration of (2) is 0.8mol/L, the temperature is 98 ℃, and a mixture of cyclohexanol and cyclohexanone is generated;
the mixture 211 of the decomposition liquid and alkali water from the top of the decomposition tower 21 enters the heterogeneous decomposition separator 22 for separation, the decomposition liquid 221 containing 70ppm of cyclohexyl hydroperoxide from the top of the heterogeneous decomposition separator 22 is washed with water and then deoxidized and decomposed into a heat exchanger; the waste lye containing 0.8mol/L sodium hydroxide coming out of the bottom of the heterogeneous decomposition separator 22 is divided into 2 parts, and a part of 78000Kg/h waste lye 222 is returned to the heterogeneous decomposition tower 21; another portion 17500Kg/h of waste lye 223 is sent to waste lye evaporation.
The detection shows that the cyclohexyl hydroperoxide conversion rate of the embodiment is 99.7%, the yield of the alcohol ketone is 93%, the cyclohexane consumption of the device is 980 Kg/ton of crude alcohol ketone, and the continuous running time of the homogeneous decomposition section is 12 months.
Example 2
In the decomposition of cyclohexylhydroperoxide of this example, a two-step decomposition process in which an acidic quasi-homogeneous catalytic decomposition process and a sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process were combined was used, and the reaction materials and process conditions were the same as in example 1, except that the aqueous solution of chromic acid containing 3% by weight was replaced with a cyclohexane solution of t-butyl chromate containing 3% by weight, as compared with the decomposition process of example 1.
The detection shows that the cyclohexyl hydroperoxide conversion rate of the embodiment is 99.7%, the yield of the alcohol ketone is 92.5%, the cyclohexane consumption of the device is 985 Kg/ton of crude alcohol ketone, and the continuous running time of the homogeneous decomposition section is 12 months.
Example 3
The embodiment uses a cyclohexane oxidation device of 5 ten thousand tons/year, and after the cyclohexane oxidation solution containing cyclohexyl hydroperoxide is concentrated, washed and dehydrated, the two-step decomposition process combining the acid quasi-homogeneous catalytic decomposition process and the sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is adopted.
Referring to fig. 2, the process flow of the cyclohexane oxidation solution containing cyclohexyl hydroperoxide of the present embodiment through concentration, washing and dehydration is as follows:
(1) Concentrating: introducing 180370Kg/h cyclohexane oxidation solution 020 with the pressure of 1.9MpaG and the temperature of 168 ℃ from a cyclohexane oxidation reactor into a cyclohexane oxidation solution pre-concentration tower 02 kettle with the pressure of 20KpaG and the temperature of 87 ℃ to perform flash evaporation concentration in the pre-concentration tower 02 kettle; the flash cyclohexane vapor releases noncondensable gases (N) dissolved in the cyclohexane oxidation solution 2 ) 022 is separated from the top of the pre-concentration tower 02 by a condensation cooling separator 01, 21000Kg/h of cyclohexane after condensation separation is used as reflux liquid 011 of the pre-concentration tower, and the other 86078Kg/h of cyclohexane 012 is returned to the front-stage oxidation to be used as a cyclohexane oxidation feed; comprehensively treating 500Kg/h of aqueous acid solution 013 after condensation and separation, and compressing tail gas by non-condensable gas 014;
(2) Washing: 93792Kg/h cyclohexane oxidation solution 021 concentrated by a pre-concentration tower 02 is sent to a washing tower 03, and is in countercurrent contact with 5000Kg/h desalted water 030 in the upper filler, water-soluble organic acid in the cyclohexane oxidation solution is washed, and 95352Kg/h cyclohexane oxidation solution 031 which is washed from the top of the tower enters the middle part of a dehydration tower 13; the washing water after washing the cyclohexane oxidation solution is in countercurrent contact with 2000Kg/h cyclohexane 033 entering from the lower part of a washing tower 03 in a filler, the cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide in the washing water are extracted by cyclohexane, and the washing water 032 after cyclohexane extraction flows out from the bottom of the washing tower to be comprehensively treated;
(3) Dehydrating: 95352Kg/h of oxidation liquid 031 from the top of the washing tower enters the middle part of the dehydration tower 13 and then contacts with cyclohexane steam and the like from the kettle of the dehydration tower 13 in a countercurrent way in a column plate, and water in the washed cyclohexane oxidation liquid is removed through alkane water azeotropy; after cyclohexane and water vapor 132 from the top of the dehydration tower are subjected to corresponding condensation cooling separation by a condensation cooling separator 15, one part of cyclohexane is used as reflux 151 of the dehydration tower, and the other part of 15352Kg/h cyclohexane liquid 152 is subjected to cyclohexane oxidation working section; the condensed and separated acidic aqueous solution 153 is comprehensively treated; the inert non-condensable gas 154 is subjected to tail gas compression and then is comprehensively treated.
When the cyclohexyl hydroperoxide of the embodiment is decomposed, the two-step decomposition process combining the acidic quasi-homogeneous catalytic decomposition process and the sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is as follows:
(1) 100Nm of 1.1Mpa after compression of a 100 Kg/h t-butyl chromate solution catalyst 111 containing 3wt% chromium with a 100 Kg/h cyclohexane solution 112 containing 3wt% 1-hydroxyethylidene-1, 1-diphosphonate (scale inhibitor) with a front end tail gas in a venturi atomizer 11 3 Atomizing the non-condensable gas 110 to form a gas mixture containing tiny catalyst solution particles, mixing the gas mixture with 80000Kg/h of concentrated and dehydrated cyclohexane oxide solution 131 from a dehydration tower 13 kettle through a pipeline, and then entering a 1 st chamber of a decomposition reactor 14; the decomposition liquid in the decomposition reactor 14 flows from the 1 chamber, the 2 chamber and the 3 chamber to the 4 chamber in sequence, the cyclohexyl hydrogen peroxide in the decomposition liquid is subjected to directional decomposition reaction under the action of a catalyst to generate cyclohexanol, cyclohexanone, a small amount of water and the like, 92% of the cyclohexyl hydrogen peroxide is decomposed in the homogeneous decomposition reactor, and the decomposition liquid 141;
the decomposition reaction releases reaction heat, so that cyclohexane is vaporized, and the cyclohexane and a small amount of acid water vapor 142 are brought into the decomposition rectifying tower 13 through a gas phase pipe;
(2) 79000Kg/h of decomposition liquid 141 (containing 0.5% of cyclohexylhydroperoxide) flowing out of the 4 chambers of the reactor (14) in the decomposition process step (1) was subjected to heterogeneous decomposition in a heterogeneous decomposition column 21; in the heterogeneous decomposition tower 21, the decomposition solution is mixed with 800Kg/h of neoalkali 210 and 20000Kg/h of circulating alkali 222 to perform decomposition reaction under the action of catalyst, and the OH of the alkaline aqueous solution is decomposed by heterogeneous catalysis - The molar concentration of (2) is 0.8mol/L, the temperature is 95 ℃, and a mixture of cyclohexanol and cyclohexanone is generated;
the mixture 211 of the decomposition liquid and alkali water from the top of the decomposition tower 21 enters a heterogeneous decomposition separator 22 for separation, and the decomposition liquid 221 containing 70ppm of cyclohexyl hydroperoxide from the top of the heterogeneous decomposition separator 22 is distilled and separated after water washing to recover cyclohexane in the decomposition liquid 221; waste lye containing 0.8mol/L sodium hydroxide from the bottom of the heterogeneous decomposition separator 22 is divided into 2 parts, and a part of 20000Kg/h waste lye 222 is returned to the heterogeneous decomposition tower 21; the other 3500Kg/h of waste lye 223 is fed to the waste lye evaporation.
The detection shows that the cyclohexyl hydroperoxide conversion rate of the embodiment is 99.7%, the yield of the alcohol ketone is 93%, the cyclohexane consumption of the device is 985 Kg/ton of crude alcohol ketone, and the continuous running time of the homogeneous decomposition section is 12 months.
Comparative example 1
Referring to fig. 3, in the present comparative example 1, the decomposition process disclosed in CN102627542B was used for the decomposition of cyclohexylhydroperoxide, and the specific steps were as follows:
(1) The cyclohexane is oxidized and the cyclohexane oxidation solution containing 436500 Kg/h cyclohexane oxidation solution 130 (pressure 1.2 MpaG, temperature 120 ℃) of cyclohexyl hydroperoxide, 3wt% of tert-butyl chromate solution 111 of 100L/h homogeneous decomposition catalyst and 3wt% of 1-hydroxy ethylidene-1, 1-diphosphonate solution 112 of 150L/h are fed into a decomposition rectifying tower 13 together through a pipeline, the pressure of the kettle of the decomposition rectifying tower 13 is 25-60 KpaG, the temperature is 90-95 ℃ for catalytic decomposition, the decomposition solution 133 containing catalyst and scale inhibitor after passing through the kettle of the decomposition rectifying tower 13 is fed into a decomposition reactor 14, and flows from 1 chamber, 2 chamber and 3 chamber to 4 chamber in sequence, and the set decomposition conversion rate of 75% is achieved through 30 minutes of residence time, so as to obtain a decomposition solution 141;
the cyclohexane is vaporized by the reaction heat, the cyclohexane and a small amount of acid water vapor 142 are brought into the decomposition rectifying tower 13 through a gas phase pipe, the cyclohexane, the water vapor and the inert gas 134 which are discharged from the top of the decomposition rectifying tower 13 are condensed, cooled and separated through a condensation cooling separator 15, 52000Kg/h cyclohexane is used as reflux 151, 130000 Kg/h cyclohexane 152 is sent back to the previous cyclohexane oxidation section, 1380 Kg/h acidic aqueous solution 153 is sent to the waste lye of heterogeneous decomposition for neutralization, and 900Nm 3 The/h inert non-condensable gas 154 is sent to a tail gas compressor, and organic matters are recovered after being pressurized by the compressor and then sent to a torch device for treatment;
(2) 305130Kg/h of decomposition solution 141 (containing 1.0% of cyclohexylhydroperoxide) flowing out of the 4 chambers of the decomposition reactor 14 is mixed with 3050Kg/h of neo-alkali 210 and 78000Kg/h of recycle alkali 222 in a heterogeneous decomposition first decomposition tower 21 and then subjected to heterogeneous decomposition reaction under the action of catalyst at low alkalinity, and the OH of the alkaline aqueous solution is decomposed by heterogeneous catalysis - The molar concentration of (2) is 0.4mol/L, and the temperature is 90 ℃;
the mixture 211 of the decomposing liquid and the alkali water, which is discharged from the top of the first decomposing tower 21, enters the heterogeneous decomposing separator 22 for separation, the waste alkali liquid containing 0.3mol/L of sodium hydroxide, which is discharged from the bottom of the heterogeneous decomposing separator 22 in the first step, is divided into 2 parts, one part of the circulating alkali liquid 222 with the concentration of 78000Kg/h is returned to the heterogeneous decomposing first decomposing tower 21, and the other part of the circulating alkali liquid 222 with the concentration of 18500Kg/h is sent to the waste alkali evaporation; the decomposing liquid 221 containing 0.06% of cyclohexyl hydroperoxide from the top of the heterogeneous first-step decomposing separator 22, 45000Kg/h recycle alkali 242 containing 1.2mol/L sodium hydroxide from the bottom of the heterogeneous second-step decomposing separator 24, and 1300Kg/h 32% of neo-alkali 230 are mixed to enter the heterogeneous second fraction Jie Da for heterogeneous decomposition reaction under the second-step high alkalinity, and the OH of the alkaline aqueous solution is decomposed by heterogeneous catalysis - The molar concentration of (2) is 1.2mol/L, the temperature is 91 ℃, and a mixture of cyclohexanol and cyclohexanone is generated;
the decomposed liquid 231 from the second fraction Jie Da is mixed with alkali water and enters a heterogeneous decomposition second-step decomposition separator 24 for separation, the decomposed liquid 241 containing less than 70ppm of cyclohexyl hydrogen peroxide is discharged from the top of the heterogeneous decomposition second-step decomposition separator 24, and cyclohexane in the decomposed liquid 241 is recovered by distillation separation after water washing; the alkali water containing 1.2mol/L sodium hydroxide which comes out from the bottom of the second-step decomposition separator 24 is divided into 2 parts as recycle alkali, and a part of the recycle alkali 242 is returned to the second part Jie Da; another portion of the recycle base 243 is returned to the first decomposition column 21.
According to detection, the conversion rate of the cyclohexyl hydroperoxide in the comparative example 1 is 99.7%, the yield of the alcohol ketone is 92%, the cyclohexane consumption of the device is 1010 Kg/ton of crude alcohol ketone, and the continuous running time of the homogeneous decomposition section is 8 months.
Comparative example 2
The comparative example adopts a technological process of introducing cyclohexyl hydroperoxide homogeneous decomposition disclosed by French Rodieya company, and the cyclohexane oxidation solution containing cyclohexyl hydroperoxide is concentrated, washed and dehydrated before entering homogeneous decomposition.
Referring to fig. 4, the specific process flow of the cyclohexane oxidation solution containing cyclohexyl hydroperoxide of the present comparative example through concentration, water washing and dehydration is as follows:
(1) Concentrating: introducing 178570Kg/h cyclohexane oxidation solution 020 with the pressure of 1.9MpaG and the temperature of 168 ℃ from a cyclohexane oxidation reactor into a cyclohexane oxidation solution pre-concentration tower 02 kettle with the pressure of 20KpaG and the temperature of 87 ℃ to perform flash evaporation concentration in the pre-concentration tower 02 kettle; the flash cyclohexane vapor releases noncondensable gases (N) dissolved in the cyclohexane oxidation solution 2 ) 022 is separated from the top of a pre-concentration tower 02 by a condensation cooling separator 01, 21000Kg/h of cyclohexane after condensation separation is used as reflux liquid 011 of the pre-concentration tower, and the other part 012 cyclohexane 86078Kg/h is returned to the front-stage oxidation to be used as feed for cyclohexane oxidation; the aqueous solution 013 of 500Kg/h acid after condensation and separation was subjected to a comprehensive treatment to obtain 400Nm 3 Performing tail gas compression on non-condensable gas 014;
(2) Washing: 93792Kg/h cyclohexane oxidation solution 021 after concentrating in a tower kettle of a pre-concentration tower 02 is sent to a washing tower 03, and is in countercurrent contact with 5000Kg/h desalted water 030 in a filler at the upper part, water-soluble organic acid in the cyclohexane oxidation solution is washed, and 95352Kg/h cyclohexane oxidation solution 031 after washing from the top of the tower enters the middle part of a dehydration tower 13; the washing water after washing the cyclohexane oxidation solution is in countercurrent contact with 2000Kg/h cyclohexane 033 entering from the lower part of a washing tower 03 in a filler, the cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide in the washing water are extracted by cyclohexane, and the washing water 032 after cyclohexane extraction flows out from the bottom of the washing tower to be comprehensively treated;
(3) Dehydrating: 95353Kg/h of oxidation liquid 031 from the top of the washing tower enters the middle part of the dehydration tower 13 and then contacts with cyclohexane steam and the like from the kettle of the dehydration tower 13 in a countercurrent way in a column plate, and water in the washed cyclohexane oxidation liquid is removed through alkane water azeotropy; after cyclohexane and water vapor 132 from the top of the dehydration tower 13 are subjected to corresponding condensation cooling separation by a condensation cooling separator 15, one part of cyclohexane is used as reflux 151 of the dehydration tower, and the other part of 15352Kg/h cyclohexane liquid 152 is used as feed for cyclohexane oxidation; comprehensively treating the condensed and separated acid water 153; the non-condensable gas 154 is subjected to tail gas compression and then is comprehensively treated.
The process flow of the cyclohexane oxidation solution containing cyclohexyl hydroperoxide of the comparative example after concentration, water washing and dehydration is carried out again for homogeneous decomposition is as follows:
80000Kg/h cyclohexane oxidation solution 131 from the tower bottom of a dehydration tower 13 and 100L/h of catalyst tert-butyl chromate 111 solution containing 3wt% of chromium enter a 1 st chamber of a decomposition reactor 14, the decomposition solution in the decomposition reactor 14 flows from the 1 st chamber, the 2 nd chamber and the 3 rd chamber to the 4 th chamber in sequence, 15L/h octyl phosphate scale inhibitor 112 is added from the upper part of the homogeneous decomposition reactor 14, and cyclohexyl hydrogen peroxide in the decomposition solution is decomposed under the action of the catalyst to generate cyclohexanol, cyclohexanone, a small amount of water and the like;
the decomposition reaction releases reaction heat, so that cyclohexane is vaporized, and the cyclohexane and a small amount of acid water vapor 142 are brought into the dehydration tower 13 through a gas phase pipe; 92% of the cyclohexylhydroperoxide was decomposed in the homogeneous decomposition reactor to produce a mixture of cyclohexanol and cyclohexanone, and 79000Kg/h of decomposed solution 141 flowing out from the 4-chamber of the reactor 14 was distilled off to recover cyclohexane in the decomposed solution.
As a result, the conversion rate of the cyclohexyl hydroperoxide in comparative example 2 was 92%, the yield of the alcohol ketone by the homogeneous decomposition reaction was 94%, but about 8% of the non-decomposed cyclohexyl hydroperoxide was decomposed under the condition of acidic high temperature in the cyclohexane rectifying tower, and the yield of the generated black tar and alcohol ketone was almost zero, so that the total yield of the alcohol ketone by the decomposition of the cyclohexyl hydroperoxide was only 86.5%, the cyclohexane consumption of the apparatus was 1060 Kg/ton of crude alcohol ketone, and the continuous start-up time of the homogeneous decomposition section was 4 months.
TABLE 1 Experimental data and relevant parameter test result data for examples 1-3 and comparative examples 1-2
Compared with the traditional homogeneous decomposition reaction, the invention uses water-soluble transition metal salts such as chromic acid aqueous solution and the like to replace tert-butyl chromate to be used as a homogeneous decomposition catalyst of cyclohexyl hydroperoxide, changes the using mode of the catalyst, adopts the combination of homogeneous decomposition and heterogeneous decomposition, and can effectively improve the cyclohexyl hydroperoxide decomposition conversion rate and the alcohol ketone yield.
Claims (16)
1. A method for producing a mixture of cyclohexanol and cyclohexanone by using cyclohexyl hydroperoxide comprises the steps of carrying out non-catalytic oxidation on cyclohexane by using molecular oxygen to generate a cyclohexyl hydroperoxide-containing cyclohexane oxidation solution, and then decomposing the cyclohexyl hydroperoxide to generate a mixture of cyclohexyl alcohol and cyclohexanone, and is characterized in that when the cyclohexyl hydroperoxide-containing cyclohexane oxidation solution is decomposed, a two-step decomposition process combining an acidic quasi-homogeneous catalytic decomposition process and a sodium hydroxide alkaline aqueous solution heterogeneous catalytic decomposition process is adopted:
(1) Atomizing the transition metal catalyst solution by using compressed gas through a Venturi atomizer, then mixing the atomized transition metal catalyst solution and cyclohexane oxidation solution containing cyclohexyl hydroperoxide through a Venturi mixer, and then, feeding the mixture into a decomposition rectifying tower, wherein the pressure of the rectifying tower is 25-60 KpaG, the temperature is 90-95 ℃, and carrying out acidic quasi-homogeneous catalytic decomposition to obtain a decomposed solution;
(2) And (3) carrying out heterogeneous catalytic decomposition on the decomposition solution obtained in the step (1) in a sodium hydroxide alkaline aqueous solution to obtain a mixture of cyclohexanol and cyclohexanone.
2. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 1, wherein in the decomposing step (1), the transition metal catalyst is a water-soluble salt of one or more transition metals selected from the group consisting of chromium, cobalt, iron, manganese, molybdenum and vanadium.
3. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 1, wherein in the decomposing step (1), the transition metal catalyst is 1-3 wt% chromic acid aqueous solution.
4. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 1, wherein in decomposition process step (1), the transition metal catalyst is an oil-soluble ester or salt of one or more transition metals of transition metals chromium, cobalt, iron, manganese, molybdenum and vanadium.
5. The method for producing a mixture of cyclohexanol and cyclohexanone by using cyclohexyl hydroperoxide according to claim 1-4, wherein in the decomposing step (1), the amount of the transition metal catalyst is 4-20 ppm by mass of cyclohexane oxidation solution.
6. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to any of claims 1-4, wherein in step (1) of the decomposition process, 1-hydroxyethylidene-1, 1-diphosphonate is added during the catalytic decomposition.
7. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 6, wherein the mass ratio of 1-hydroxyethylidene-1, 1-diphosphonate to transition metal catalyst is 1:0.6-1.4.
8. The method for producing a mixture of cyclohexanol and cyclohexanone by cyclohexylhydroperoxide according to any of claims 1-4, wherein in decomposition process step (2) the aqueous alkaline solution has OH - The molar concentration of (C) is 0.5-1.0mol/L.
9. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 5, wherein in decomposition process step (2), the aqueous alkaline solution has OH - The molar concentration of (C) is 0.5-1.0mol/L.
10. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 6, wherein in decomposition process step (2), the aqueous alkaline solution has OH - The molar concentration of (C) is 0.5-1.0mol/L.
11. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 7, wherein in decomposition process step (2), the aqueous alkaline solution has OH - The molar concentration of (C) is 0.5-1.0mol/L.
12. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to any of claims 1-4, wherein in decomposition process step (2) the heterogeneously catalyzed decomposition temperature is 95-105 ℃.
13. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 5, wherein in decomposition process step (2), the heterogeneously catalyzed decomposition temperature is 95-105 ℃.
14. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 6, wherein in the decomposing step (2), the heterogeneously catalyzed decomposition temperature is 95-105 ℃.
15. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 7, wherein in decomposition process step (2), the heterogeneously catalyzed decomposition temperature is 95-105 ℃.
16. The method for producing a mixture of cyclohexanol and cyclohexanone from cyclohexylhydroperoxide according to claim 8, wherein in decomposition process step (2), the heterogeneously catalyzed decomposition temperature is 95-105 ℃.
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